Process of preparing a material having prolonged scent retaining characteristics andproduct thereof



Patented June 23, 1953 UNITED STATES PATENT OFFICE UCT THEREOF Roger W. Philippin, Babylon, N. Y.

No Drawing. Application May 5, 1950, Serial No. 160,394

7 Claims.

My present invention relates to a process of preparing a material having prolonged scent retaining characteristics, and more particularly, for preparing such a material, which may be admixed with various other known types of ma terials or compounds to provide a scent which will be relatively mild when initially exposed to air, yet which will retain its scent for a substantial period of time such as five days to a week. The present invention also includes the product of the process aforesaid. This novel material is based primarily on known types of perfumes, and particularly upon various mixtures of known essential perfume oils, which have been used for many years. It has been found, however, in the use of such hitherto known and available materials, that the scent therefrom is particularly pronounced upon the initial exposure to air and is quite rapidly dissipated, so that at the end of a day or less, none of the scent remains.

An important object of the present invention is to provide a material, which may be made from selected mixtures of known natural essential perfume oils or similar starting materials, which will have a relatively less pronounced scent upon its inital exposure to air, yet will have prolonged scent retaining characteristics, so that the dissipation of the scent occurs over a substantially long period of time, for example, five days to a week. In this way, such known materials as, for example, nail polish may be provided or have admixed therewith scented material prepared in accordance with the present invention, such materials upon use, will have its characteristic scent perceptible following the initial evaporation of the solvent normall used in such nail polish material, with the scent being retained for a long period of time. The present invention is particularly directed to the making of a scented material, which may thereafter be added to or be in any suitable manner admixed with various other known types of materials, for example, nail polish.

Summarizing the present invention, there is provided a process by which a mixture of natural essential perfume oils, of the type which contain terpenes, is first mixed with an aliphatic alcohol, having from three to five carbon atoms in the proportion of about one volume of the mixed perfume oils to about one-half to twice said volume of the alcohol. The mixture so prepared is then fractionally distilled, preferably using a distilling column, to produce the following separate distillate fractions: (a) an alcohol fraction distilling off at about boiling point of the aliphatic alcohol used, (1)) a fraction boiling at atmospheric pressure in a range of about 140 to about 148 C., (c) a fraction boiling at atmospheric pressure in the range of about 195 to 200 C'., and (d) a fraction boiling at atmospheric pressure at a temperature of about 220 C. Following the distillation and separation of the several fractions aforesaid, there remains in the distilling vessel a residue. The next step is that of subjecting the residue and the fractions (b), (c) and (d) aforesaid to a saponification action, by introducing this residue and these fractions separately into an alcohol solution of a caustic alkali. Preferably, but not necessarily, there is also introduced separately into the alcohol solution of caustic alkali a ketone, which is preferably either one or both of the following ketones: methyl. hexyl ketone [CH3-CO-(CH2)5CH3] and methyl heptyl ketone [CH3'CO'(CH2)6'CH3]. The de tails of the several steps of the process will be separately discussed hereinafter.

The first consideration in this process is the starting material. It has been found by considerable research that the starting material must include a major amount, at least, of natural essential perfume oils, as distinguished from synthetic perfume oils. Such natural oils, as a general rule and in accordance with the present invention, must contain terpenes, as this seems to be an essential characteristic of the ingredient materials required for the successful practice of the process of this invention. The types of perfume oils which may be used in different mixtures may be widely varied, as is illustrated by the examples of different combinations thereof hereinafter given. The mixing of perfume oils to get desired scents is an ancient art known to perfumers. Different mixtures obviously give different characteristic scents. The only essential requirements. from the point of View of the present invention, are that the mixture prepared in accordance with the desires of a perfumer shall have as its essential ingredients, natural essential perfume oils containing terpenes, at least to a major extent, that is, to an extent of more than'50% of the total starting mixture. Within these limitations, any desired mixture of perfume oils may be used as the starting material in the practice of the process of the present invention.

The first operation in the practice of the process is to mix the perfume oils with an aliphatic alcohol having from 3 to 5 carbon atoms, in the proportion of about 200 volumes of the mixed perfume oils to from about to about 400 volumes of the alcohol. While any of the aliphatic alcohols, having from 3 to 5 carbon atoms inclusive, may be used in the practice of the present process, I have found that normal butyl alcohol is usually preferred.

The next step of the process is to effect a fractional distillation, preferably using a distilling vessel from which the vapors pass usually upwardly into a reflux or distilling column having an outlet adjacent to the top thereof for vapors passing from the distilling apparatus. This particular apparatus is not necessarily essential, but is efficacious of making a separation of different materials having different boiling points. Inasmuch as equipment of this kind is well known for laboratory use and as commercial equipment equivalent thereto is similarly well known, no illustration of this equipment is thought necessary. Any suitable equipment in which a fractional distillation can be carried out may be used in the practice of this part of the process.

The first fraction to be separated from the mixture in the distilling vessel is what might be termed the alcohol fraction (a), which contains substantially all the alcohol originally added to and. mixed with the perfume oils. This fraction boils off at about the boiling point of the particular alcohol used. It is usually inevitable that some materials will boil off with the alcohol, due to partial pressure in a manner similar to the well known steam distillation. I have found, for example, when using 200 cc. mixed perfume oils and about 150 cc. of alcohol, the total alcohol fraction (a) is about 160 to about 165 cc., indicating that something in addition to the alcohol is separated during this step of the process. I have further found that if this fraction be separately fractionally distilled, I have been able to obtain about 18 grams of material of a more or less solid nature, which has originally distilled over with the alcohol and which may later be separated therefrom. by a separate fractional distillation, the material remaining as a residue in the separate fractional distillation of the alcohol.

While it might seem to be needless to add alcohol and then separate this alcohol from the rest of this material by fractional distillation, it is my present theory that some reaction probably occurs in the original essential oil material as a result of the practice of that portion of that process thus far particularly described. Exactly what this reaction or reactions may be is not known to me at this time; nor is the exact character of the material distilling off with the alcohol known. In any event, I have found that the initial step of mixing the alcohol as aforesaid and then fractionally distilling it off as an alcohol fraction (a) is essential to the practice of the process of this invention.

, Following the separation of the first fraction or alcohol, the process as to all the essential oils tried, including the examples hereinafter given, follows the following procedure. It is possible that some essential oils having different original constituents would give somewhat different fractions respectively. The temperature of the boiling material is rapidly raised to a temperature in the range of about 140 to 148 C. In this temperature range a second fraction (2)) is removed and segregated. This second fraction (1)) in the case of many, if not all, essential oils is believed to be principally anthranilic acid (o-amino benzoic acid). The distillation of this fraction, and in fact the entire distillation, is normally carried on at substantial atmospheric pressure. It will be obvious that if the pressure of the distillation be changed materially from atmospheric, the temperatures would have to be adjusted accordingly. However, unless the pressures and temperatures be changed to a very substantial extent, the same results will ensue as are particularly described in the present disclosure.

The next fraction (0) to be separated when using many, if not all, essential oils is one coming off at atmospheric pressure in the range of about 195 to about 200. This fraction (c) is believed to be principally l-linalool, although it may contain a substantial amount of the similar compound d-linalool, the latter also being known as Coriandrol.

The next fraction ((1) which is separted in the fractional distillation of many, if not all, essential oils is one which boils at atmospheric pressure at a temperature of about 220 C. This fraction is believed to contain principally linalyl acetate, which compound is sometimes also known as bergamol.

While as to the several fractions aforesaid there is stated what is believed to be the principal ingredient of each, this statement is made in order fully to set forth the applicants present knowledge of the process, for what it may be worth and is to be considered the theory of the operation or process. Applicant does not, however, rely upon this theory or the correctness of his analyses of the ingredients in question in this case, but rather upon the general directions for carrying out the process and the results to be obtained therefrom. When the process is carried out as herein taught, reproducible results are obtained; and these results are the desired results in accordance with the present invention.

Following the separation of the several fractions aforesaid there remains in the distilling vessel or chamber, a residue which is semi-solid in character and the exact composition of which is unknown. This residue, however, is important in the process as hereinafter set forth.

In the ordinary practice of the process the next step is to saponify the products of the fractional distillation as aforesaid. This is effected by separately introducing the residue and the fractions (b), (c) and (d) aforesaid into an alcohol solution of a caustic alkali.

Considering first the composition of the caustic alkali to be used and the amount thereof, it is found that both sodium hydroxide and potassium hydroxide are usable with the present process. The preferred composition, in accordance with this process, is, however, a mixture of the two. The reason for this is that when sodium hydroxide alone is used, the resultant material is in the form of relatively hard crystals, usually highly alkaline in character and usually tending to have a relatively dark color. Such material is usable to some extent in the noncosmetic field, that is where it does not have to come into contact with some part of the human body. For example, it would not be appropriate, as I now visualize it, in different kinds of cosmetic and/or nail polish. It might, however, be used with shoe polish, paints, lacquers, and some types of detergents.

On the other hand, if the caustic alkali used were solely potassium hydroxide, the resulting product would tend to be quite soft or semiliquid in character, rather than crystalline. Here again the material may be used for certain purposes, although when used in a lacquer such as nail polish, it might tend to prevent the complete drying of the lacquer.

By using a desired mixture of sodium and potassium hydroxides, a final product having an intermediate character may be prepared, that is, one which will be neither too hard nor too soft, which will be light tan in color and will not tend. to darken any material with which it may be mixed. This desired intermediate mixture may be used satisfactorily in many types of cosmetics, and particularly in nail polish.

By carefully controlling the amount of caustic alkali, used in respect to the amount of materials to be saponified therewith, it is possible to obtain a product which i only slightly on the alkaline side of neutral, for example, one having a pH of about 8. This is so close to neutral that for all practical purposes it may be considered neutral, and may be used in any place where an alkaline material would be unsatisfactory and where substantial neutral material may be required. Using the same example as used above, that is starting with 200 cc. of essential oils, I have found that a mixture of cc. of 78% NaOH in ethyl alcohol and cc. of 45 Be. KOH in ethyl alcohol makes a satisfactory mixture for use in th particular saponification described to make a product usable in cosmetics, for example, in nail polish.

. In effecting the saponification, it has been found that the residue from the entire fractional distillation and the fractions (b), (c) and (d) above described must be introduced separately into the alcohol solution of caustic alkali. The reason for this is unknown. The separate introduction is, however, essential. The residue and the fractions (1)), (c) and (d) may be introduced in any desired order as between themselves, although normally the residue is first introduced and then the fractions (b), (c) and (d) in any order. In effecting such introduction, each of these materials are added separately to the alcohol solution of caustic alcohol and then a predetermined time permitted to elapse subsequent to the addition of each and prior to the introduction of the next to be added for the apparent completion of any reaction occurring upon each such introduction. The reaction taking place is believed to be a start at least of a saponification reaction. The exact chemical nature of the reaction as to any and all fractions and the residue is not known, however; and no theory can be expressed positively in respect thereto. However, as each fraction and/or the residue is separately introduced, a reaction seems to occur of a visible character. The fact that some reaction occurs upon addition of the residue and at least one of the distillate fractions (b), (c) and (d) is proven by the fact that upon some of such additions, the temperature of the mixed material rises to some extent. However, as a practical matter, it is proper and satisfactory to introduce each of the distillate fractions and the residue separately and to leave a time period of about 5 to 10 minutes between each such introduction. Following the completion of the saponification, the resulting material may be dried in air to give the final product, which has the appearance of light brown sugar, being crystalline in character and yet somewhat resinous as distinguishedfrom hard crystals, at least where mixtures of sodium and potassium hydroxides are used as the alkali.

There has been described the minimum requirements for carrying on the process of the present invention. It may be noted that the alcohol fraction (a) and the material coming over with it was not introduced into the saponification in accordance with the minimum process requirements. This fraction (0.) may be disposed of .in any one of several ways. It may, of course,

be discarded; however, that is not usually desired. If one is making but a single batch of the material in accordance with the present process, the alcohol fraction (a) may be separately redistilled as aforesaid, and the residue therefrom added into the saponification step of the process separately, and in the same way that the residue from the entire distillation was sepa-- rately added to alcoholic caustic alkali. If, on the other hand, a repeated series of batches is to be made, it has been found practical and is a preferred embodiment of the present invention to use the alcohol fraction ((1) from a first batch as the alcohol to be mixed with the essential oil mixture in th preparation of the next or a suc ceeding batch. In this way, it is unnecessary eparately to distill the alcohol fraction (0.) and this step of the process is saved in the making of succeeding batches. The material passing over with the alcohol in the first of a series of batches is reintroduced with the alcohol into the next or a succeeding batch in which the alcohol along with any material therein is used. In this way, all this material is resupplied to the process and finds its way into the final product as will now be obvious to those skilled in the art.

Again while the process may be practiced according to the minimum requirements as aforesaid, it i usually preferred to add into the saponification step an additional material, namely, a ketone or some material equivalent thereto from the point of view of the present process. Preferred materials, in accordance with the present invention for addition to the saponification step of the process consist of methyl hexyl ketone [CHrCO-(CHzM-CI-Ia] and methyl heptyl ketone [CH3'CO'(.CH2)a-CH31. These two ketones are by no means the only ones which may be added at this step of the process. It is contemplated, therefore, that any suitable material or none at all may be added at this stage in the making of the final product- The product is satisfactory without any such addition and may be satisfactorily made with a substantial number of different materials, only two of which are herein particularly disclosed.

Again, while the order of adding the several materials to the alcohol solution of caustic alkali I is not critical, it is normal in the practice of the present process to add the ketone or any equivalent thereof, if used, after the other materials have been added and separately therefrom. Where no ketone or equivalent material is used at this stage of the process, the amount of alkali to be used must be adjusted accordingly. The example actually given wherein 30 cc. of mixed NaOH and KOH is used is calculated so as to include the addition of about 50 cc. of methylhexyl ketone. The product resulting in this particular example after drying weighed about 194 grams.

Following the separate addition of the several materials to the alcohol solution of caustic alkali as aforesaid, the mixed materials may be caused to complete their saponification reaction by boiling under reflux conditions, for example, for about two hours. This practically assures the completion, to the extent possible, of the saponification reactions.

The characteristics of the final product, other aforesaid for the reasonthat there is no way presentlyknown of describing this composition except by the process of making it. It has been found that the product is soluble in alcohol and in some organic solvents. It is only slightly soluble in water. When completely dried, it is a crystalline substance resembling light brown sugar in appearance and being light tan in color. It is compatible and miscible with many organic materials such as paints, and lacquers, with many of the bases used as cosmetics and with other analogous materials. It may find many uses, not only in nail polish, as particularly described, but also in lacquers for various purposes, paints, detergents, cosmetics of diiierent kinds and innumerable othor things, only a few of which have thus far been visualized.

Examples of different combinations of natural essential perfume oils which may b processed as specifically herein are as follows (the figure given as to each ingredient being volumetric proportions) cc. Rose oil 15 Sandalwood 65 Vetiver oil 35 Neroli 15 Jasmine Bergamot 20 Balsam Peru Labdanum 25 cc. Niaouli 30 Nerol 25' Tuberrose Oil of Convolvulus scoparius Ylang ylang 35 Yndol 15 Eugenol 45 Verbena 5 III Vetiverol 4O Seringa 20 Sweet almond 25 Rosemary 15 Sage 25 Orange flower Lavender 20 Oil of lemon 25 cc. Ar'sarum 15 Myrcia 25 Melissa 15 Geranium 65 Patchouli 25 Heliotrope vl0 Cedar wood 30 Acacia 15 cc. Angelica root Thibetolide 25 Cardamon 40 Cajuput l5 Terpinyl acetate 10 Gardina 10 Valerian 5 Terpineol 60 Santalol 50 Rhodinol 20 Orris root 35 Piperitone 15 Eucalyptus 25 Aleppo 20 Safrole 30 Champaca 5 VII Nerolidol 65 Wintergreen 35 Calamus 15 Eugenol 25 Mandarin 10 Boronaia 5 Irisone 15 Oak moss 30 While there is herein disclosed but one principal process and certain variants thereof, the essential characteristics of each ingredient and each step of the process have been set out to the best of my present knowledge. It is contemplated, however, that equivalents may be substituted wherever appropriate and as will occur to those skilled in the art from the foregoing disclosure. I do not wish to be limited, therefore, except by the scope of the appended claims, which are to be construed validly as broadly as the state of the prior art permits.

What is claimed is:

1. The process of preparing a scented material having prolonged scent retaining characteristics from a starting material, the essential active ingredients of which consist of a mixture of natural essential perfume oils which contain terpenes, said process comprising the steps of mixing with a volumetric quantity of said starting material from about half to about twice said volumetric quantity of an aliphatic alcohol having from 3 to 5 carbon atoms, fractionally distilling the mixture so formed to, produce as separate distillate fractions: ((1) an alcohol fraction distilled oil at about the boiling point of said aliphatic alcohol, (1)) a fraction boiling at atmospheric pressure in the range of about C. to about 148 C., (c) a fraction boiling at atmospheric pressure in the range of about C. to about 200 C., and (d) a fraction boiling at atmospheric pressure at a temperature of about 220 C., and leaving a residue; and subjecting said residue and said fractions (b), (c) and (d) to a saponification action by introducing said residue and said fractions (b), (c) and (d) separately into an alcohol solution of a caustic alkali to produce the desired scented material.

2. The process in accordance with claim 1, wherein said aliphatic alcohol is n-butyl alcohol.

3. The process in accordance with claim 1, comprising in addition, separating said alcohol fraction (a) into two parts, consisting of (1) the alcohol and (2) the material which separated in the original fractional distillation with the alcohol, and in the step of subjecting the residue and said fractions (b), (c) and (d) to a saponification action, also introducing the material (2) separated from said alcohol fraction separately into the alcohol solution of caustic alkali.

4. The process in accordance with claim 1, when used in the making of a plurality of batches in accordance with said process, comprising the additional step of using alcohol fraction (a) separated from one batch as the aliphatic alcohol to be mixed with the starting material in the processing of a subsequent batch, whereby any material distilling over with the alcohol fraction in said one batch will be returned to the distillation of said subsequent batch.

5. The process in accordance with claim, 1, wherein said caustic alkali is sodium hydroxide.

6. The process in accordance with claim 1, wherein said caustic alkali is potassium hydroxide.

7. A material having prolonged scent retaining characteristics prepared by the process of claim 1.

ROGER W. PHILIPPIN.

10 References Cited in the tile 0! this patent UNITED STATES PATENTS Number Name Date 1,878,477 Ellis Sept. 20, 1932 OTHER REFERENCES Thomssen: Modern Cosmetics, 3d edition 

1. THE PROCESS OF PREPARING A SCENTED MATERIAL HAVING PROLONGED SCENT RETAINING CHARACTERISTICS FROM A STARTING MATERIAL, THE ESSENTIAL ACTIVE INGREDIENTS OF WHICH CONSIST OF A MIXTURE OF NATURAL ESSENTIAL PERFUME OILS WHICH CONTAIN TERPENES, SAID PROCESS COMPRISING THE STEPS OF MIXING WITH A VOLUMETRIC QUANTITY OF SAID STARTING MATERIAL FROM ABOUT HALF TO ABOUT TWICE SAID VOLUMETRIC QUANTITY OF AN ALIPHATIC ALCOHOL HAVING FROM 3 TO 5 CARBON ATOMS, FRACTIONALLY DISTILLING THE MIXTURE SO FORMED TO PRODUCE AS SEPARATE DISTILLATE FRACTIONS: (A) AN ALCOHOL FRACTION DISTILLED OFF AT ABOUT THE BOILING POINT OF SAID ALIPHATIC ALCOHOL, (B) A FRACTION BOILING AT ATMOSPHERIC PRESSURE IN THE RANGE OF ABOUT 140* C. TO ABOUT 148* C., (C) A FRACTION BOILING AT ATMOSPHERIC PRESSURE IN THE RANGE OF ABOUT 195* C. TO ABOUT 200* C., AND (D) A FRACTION BOILING AT ATMOSPHERIC PRESSURE AT A TEMPERATURE OF ABOUT 220* C., AND LEAVING A RESIDUE; AND SUBJECTING SAID RESIDUE AND SAID FRACTIONS (B), (C) AND (D) TO A SAPONIFICATION ACTION BY INTRODUCING SAID RESIDUE AND SAID FRACTIONS (B), (C) AND (D) SEPARATELY INTO AN ALCOHOL SOLUTION OF A CAUSTIC ALKALI TO PRODUCE THE DESIRED SCENTED MATERIAL. 